Indole-3-thio­uronium nitrate

Lutz, M.; Spek, A.L.; Geer, E.P.L. van der; Koten, G. van; Klein Gebbink, R.J.M.

doi:10.1107/S1600536807064707

organic compounds

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Volume 64| Part 1| January 2008| Page o194

https://doi.org/10.1107/S1600536807064707

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Indole-3-thiouronium nitrate

Martin Lutz,^a Anthony L. Spek,^a ^* Erwin P. L. van der Geer,^b Gerard van Koten ^b and Robertus J. M. Klein Gebbink ^b

^aCrystal and Structural Chemistry, Bijvoet Center for Biomolecular Research, Faculty of Science, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands, and ^bChemical Biology & Organic Chemistry, Faculty of Science, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands
^*Correspondence e-mail: a.l.spek@chem.uu.nl

(Received 29 November 2007; accepted 30 November 2007; online 6 December 2007)

In the title compound, C₉H₁₀N₃S⁺·NO₃⁻, the indole ring system and the thiouronium group are nearly perpendicular, with a dihedral angle of 88.62 (6)°. Hydrogen bonding generates two-dimensional networks which are linked to each other via π stacking interactions of the indole groups [average inter-planar ring–ring distance of 3.449 (2) Å].

Related literature

For reviews of the supramolecular chemistry of thiourea derivatives, see: Takemoto (2005 ); Fitzmaurice et al. (2002 ); Schmidtchen & Berger (1997 ). For anion recognition of thiouronium salts, see: Esteban Gómez et al. (2005 ). For the synthesis of the title compound, see: Harris (1969 ); van der Geer et al. (2007 ). For thermal motion analysis, see: Schomaker & Trueblood (1998 ).

Experimental

Crystal data

C₉H₁₀N₃S⁺·NO₃⁻
M_r = 254.27
Orthorhombic, P b c a
a = 12.0524 (2) Å
b = 8.7395 (1) Å
c = 21.1893 (3) Å
V = 2231.91 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 150 (2) K
0.30 × 0.24 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
32180 measured reflections
2563 independent reflections
2120 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.089
S = 1.04
2563 reflections
194 parameters
All H-atom parameters refined
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.880 (18)	2.036 (19)	2.8290 (16)	149.4 (16)
N2—H2N⋯O1	0.87 (2)	2.00 (2)	2.8679 (17)	174.2 (16)
N2—H3N⋯O2ⁱⁱ	0.90 (2)	2.108 (19)	2.9013 (16)	147.0 (16)
N3—H4N⋯O2	0.90 (2)	2.00 (2)	2.8966 (19)	172.5 (19)
N3—H5N⋯O3ⁱⁱⁱ	0.89 (2)	2.10 (2)	2.8817 (17)	145.0 (18)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1999 ); cell refinement: HKL-2000 (Otwinowski & Minor, 1997 ); data reduction: HKL-2000; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807064707/bt2657sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064707/bt2657Isup2.hkl

checkCIF report

Comment top

Thiourea derivatives have found widespread application in molecular recognition and supramolecular chemistry, largely due to their hydrogen-bonding complementarity with carboxylate groups (Takemoto, 2005; Fitzmaurice et al., 2002; Schmidtchen & Berger, 1997). Of all thiourea derivatives, positively-charged thiouronium salts may be among the strongest anion receptors due to their increased acidity and the electrostatic stabilization of the anion-receptor complex (Esteban Gómez et al., 2005). Recently, we have demonstrated that N-substituted indole-3-thiouronium salts are readily available from indole by nucleophilic substitution at the nitrogen atom followed by electrophilic aromatic substitution with thiourea (van der Geer et al., 2007). In order to gain more insight into the hydrogen-bonding properties of indole-3-thiouronium salts, we have obtained the crystal structure of the title compound indole-3-thiouronium nitrate (I).

Bond distances and angles are as expected. The thiouronium group itself is planar, with the C—N bond lengths of 1.3076 (19) and 1.3162 (19) Å indicating a significant degree of double-bond character. Reflecting the resulting hindered rotation about the C—N bonds, solution-phase ¹H NMR shows separate signals for the thiouronium hydrogen atoms cis and trans to sulfur at room temperature. The least-squares plane of the thiouronium moiety forms an interplanar angle of 88.62 (6)° with respect to the least-squares plane of the indole group (Fig. 1).

A thermal motion analysis using the program THMA11 (Schomaker & Trueblood, 1998) results in a low weighted R value (R = SQRT[(Σ (wΔU)²) / (Σ (wU_obs)²)]) of 0.084 indicating that the molecule behaves as a rigid body in the solid state.

All N—H groups act as hydrogen bond donors with the oxygen atoms of the nitrate anion as acceptors. O1 and O2 accept two hydrogen bonds, respectively, while O3 accepts only one. By this hydrogen bonding scheme a two-dimensional network in the a,b-plane is formed (Fig. 2).

Via π stacking interactions the indole ring systems form parallel, centrosymmetric dimers with an average ring···ring distance of 3.449 (2) Å (Fig. 3). These π stacking interactions occur between the two-dimensional hydrogen bonded layers.

Related literature top

For reviewsof the supramolecular chemistry of thiourea derivatives, see: Takemoto (2005); Fitzmaurice et al. (2002); Schmidtchen & Berger (1997). For anion recognition of thiouronium salts, see: Esteban Gómez et al. (2005). For the synthesis of the title compound, see: Harris (1969); van der Geer et al. (2007). For thermal motion analysis, see: Schomaker & Trueblood (1998).

Experimental top

Indole-3-thiouronium iodide was prepared as described in literature (Harris, 1969). To a solution of indole-3-thiouronium iodide (0.100 g, 0.313 mmol) in EtOH (10 ml) was added AgNO₃ (0.0532 g, 0.313 mmol). The solution was stirred for 1 h, filtered to remove AgCl, and concentrated to approximately 3 ml. Ether (60 ml) was added, and after 48 h, white needles were collected by centrifugation, washed with ether, and dried in vacuo. Yield: 0.0738 g (0.290 mmol, 93%). Anal. Calcd for C₉H₁₀N₄O₃S: C, 42.51; H, 3.96; N, 22.03; S, 12.61. Found: C, 42.32; H, 4.08; N, 21.92; S, 12.73. The ¹H NMR spectrum was identical to that of indole-3-thiouronium iodide. FT—IR (ATR, ν, cm^-1): 3335, 3264, 3122, 1662, 1640, 1498, 1423, 1388, 1308, 1237, 1218, 1128, 1104, 1065, 1049, 1006, 816, 744. Crystals suitable for X-ray diffraction studies were obtained by ether vapor diffusion into an EtOH solution of the product.

Structure description top

For reviewsof the supramolecular chemistry of thiourea derivatives, see: Takemoto (2005); Fitzmaurice et al. (2002); Schmidtchen & Berger (1997). For anion recognition of thiouronium salts, see: Esteban Gómez et al. (2005). For the synthesis of the title compound, see: Harris (1969); van der Geer et al. (2007). For thermal motion analysis, see: Schomaker & Trueblood (1998).

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: HKL-2000 (Otwinowski & Minor, 1997); data reduction: HKL-2000 (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Hydrogen bonding scheme in compound (I). View along the crystallographic b axis. C—H hydrogen atoms are omitted for clarity. Symmetry operations i: 1 - x, 1/2 + y, 0.5 - z; ii: 1/2 + x, y, 0.5 - z; iii: 2 - x, 1/2 + y, 0.5 - z.
	Fig. 3. π stacking interactions between the indole ring systems in (I). View along the crystallographic a axis. Symmetry operation i: 1 - x, 1 - y, -z.

Indole-3-thiouronium nitrate top

Crystal data top

C₉H₁₀N₃S⁺·NO₃⁻	F(000) = 1056
M_r = 254.27	D_x = 1.513 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 44477 reflections
a = 12.0524 (2) Å	θ = 1.0–27.5°
b = 8.7395 (1) Å	µ = 0.29 mm⁻¹
c = 21.1893 (3) Å	T = 150 K
V = 2231.91 (5) Å³	Plate, colourless
Z = 8	0.30 × 0.24 × 0.06 mm

Data collection top

Nonius KappaCCD diffractometer	2120 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.048
Graphite monochromator	θ_max = 27.5°, θ_min = 1.9°
φ and ω scans	h = −15→15
32180 measured reflections	k = −11→11
2563 independent reflections	l = −27→27

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: difference Fourier map
wR(F²) = 0.089	All H-atom parameters refined
S = 1.04	w = 1/[σ²(F_o²) + (0.0479P)² + 0.7806P] where P = (F_o² + 2F_c²)/3
2563 reflections	(Δ/σ)_max < 0.001
194 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₉H₁₀N₃S⁺·NO₃⁻	V = 2231.91 (5) Å³
M_r = 254.27	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.0524 (2) Å	µ = 0.29 mm⁻¹
b = 8.7395 (1) Å	T = 150 K
c = 21.1893 (3) Å	0.30 × 0.24 × 0.06 mm

Data collection top

Nonius KappaCCD diffractometer	2120 reflections with I > 2σ(I)
32180 measured reflections	R_int = 0.048
2563 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.089	All H-atom parameters refined
S = 1.04	Δρ_max = 0.26 e Å⁻³
2563 reflections	Δρ_min = −0.23 e Å⁻³
194 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.69778 (3)	0.42394 (4)	0.119223 (18)	0.02623 (13)
N1	0.37464 (10)	0.47136 (15)	0.12180 (6)	0.0261 (3)
H1N	0.3086 (14)	0.448 (2)	0.1367 (9)	0.034 (5)*
N2	0.67908 (11)	0.63413 (15)	0.21093 (6)	0.0247 (3)
H2N	0.7073 (14)	0.693 (2)	0.2402 (9)	0.036 (5)*
H3N	0.6067 (17)	0.642 (2)	0.2016 (8)	0.037 (5)*
N3	0.85228 (11)	0.53570 (16)	0.19399 (7)	0.0281 (3)
H4N	0.8814 (17)	0.598 (2)	0.2236 (10)	0.049 (6)*
H5N	0.9029 (17)	0.481 (2)	0.1728 (10)	0.048 (6)*
C1	0.47062 (12)	0.40523 (18)	0.14151 (7)	0.0263 (3)
H1	0.4724 (13)	0.320 (2)	0.1715 (8)	0.030 (4)*
C2	0.55884 (11)	0.47801 (17)	0.11306 (6)	0.0224 (3)
C3	0.56104 (12)	0.70408 (16)	0.03254 (7)	0.0241 (3)
H3	0.6404 (14)	0.7099 (18)	0.0278 (7)	0.025 (4)*
C4	0.49126 (14)	0.80176 (18)	0.00043 (7)	0.0283 (3)
H4	0.5191 (15)	0.876 (2)	−0.0291 (9)	0.037 (5)*
C5	0.37534 (13)	0.79541 (18)	0.00913 (7)	0.0296 (3)
H5	0.3302 (14)	0.868 (2)	−0.0129 (9)	0.040 (5)*
C6	0.32737 (12)	0.68900 (18)	0.04876 (7)	0.0267 (3)
H6	0.2499 (15)	0.6822 (18)	0.0556 (7)	0.028 (4)*
C7	0.39845 (11)	0.58860 (16)	0.08036 (6)	0.0222 (3)
C8	0.51463 (11)	0.59550 (15)	0.07326 (6)	0.0203 (3)
C9	0.74591 (11)	0.54277 (16)	0.18022 (6)	0.0219 (3)
O1	0.78687 (8)	0.82212 (13)	0.30339 (5)	0.0302 (3)
O2	0.95458 (8)	0.75180 (13)	0.27976 (5)	0.0308 (3)
O3	0.92651 (9)	0.94570 (13)	0.34188 (5)	0.0351 (3)
N4	0.88984 (10)	0.84099 (14)	0.30879 (6)	0.0240 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0208 (2)	0.0269 (2)	0.0309 (2)	0.00496 (14)	−0.00216 (14)	−0.00352 (15)
N1	0.0191 (6)	0.0331 (7)	0.0262 (6)	−0.0050 (5)	0.0008 (5)	0.0028 (5)
N2	0.0174 (6)	0.0284 (7)	0.0284 (7)	0.0015 (5)	−0.0012 (5)	−0.0036 (6)
N3	0.0179 (6)	0.0306 (7)	0.0357 (7)	0.0028 (5)	−0.0010 (5)	−0.0007 (6)
C1	0.0244 (7)	0.0292 (8)	0.0253 (7)	−0.0031 (6)	−0.0015 (6)	0.0024 (6)
C2	0.0186 (6)	0.0248 (7)	0.0239 (7)	0.0001 (5)	−0.0017 (5)	−0.0015 (6)
C3	0.0212 (7)	0.0245 (7)	0.0265 (7)	−0.0034 (6)	0.0018 (6)	−0.0024 (6)
C4	0.0323 (8)	0.0253 (8)	0.0273 (8)	−0.0035 (6)	−0.0004 (6)	0.0022 (6)
C5	0.0311 (8)	0.0286 (8)	0.0291 (8)	0.0039 (6)	−0.0066 (6)	−0.0009 (6)
C6	0.0190 (7)	0.0326 (8)	0.0287 (8)	0.0008 (6)	−0.0038 (6)	−0.0048 (6)
C7	0.0198 (7)	0.0260 (7)	0.0207 (6)	−0.0029 (6)	−0.0005 (5)	−0.0030 (5)
C8	0.0178 (6)	0.0222 (7)	0.0209 (7)	−0.0010 (5)	−0.0001 (5)	−0.0029 (5)
C9	0.0175 (6)	0.0228 (7)	0.0255 (7)	−0.0004 (5)	−0.0009 (5)	0.0059 (6)
O1	0.0145 (5)	0.0416 (6)	0.0345 (6)	0.0011 (4)	0.0000 (4)	−0.0075 (5)
O2	0.0186 (5)	0.0431 (7)	0.0308 (6)	0.0075 (5)	0.0033 (4)	0.0002 (5)
O3	0.0293 (6)	0.0403 (7)	0.0358 (6)	−0.0102 (5)	0.0002 (5)	−0.0051 (5)
N4	0.0177 (6)	0.0309 (7)	0.0235 (6)	0.0003 (5)	0.0013 (5)	0.0042 (5)

Geometric parameters (Å, º) top

S1—C2	1.7448 (14)	C3—C4	1.378 (2)
S1—C9	1.7566 (15)	C3—C8	1.399 (2)
N1—C1	1.359 (2)	C3—H3	0.963 (17)
N1—C7	1.3795 (19)	C4—C5	1.410 (2)
N1—H1N	0.880 (18)	C4—H4	0.963 (18)
N2—C9	1.3076 (19)	C5—C6	1.380 (2)
N2—H2N	0.87 (2)	C5—H5	0.955 (19)
N2—H3N	0.90 (2)	C6—C7	1.397 (2)
N3—C9	1.3162 (19)	C6—H6	0.946 (18)
N3—H4N	0.90 (2)	C7—C8	1.4096 (19)
N3—H5N	0.89 (2)	O1—N4	1.2572 (15)
C1—C2	1.378 (2)	O2—N4	1.2628 (16)
C1—H1	0.979 (18)	O3—N4	1.2348 (16)
C2—C8	1.432 (2)

C2—S1—C9	102.23 (7)	C3—C4—H4	121.7 (11)
C1—N1—C7	109.54 (12)	C5—C4—H4	117.2 (11)
C1—N1—H1N	124.0 (12)	C6—C5—C4	121.41 (14)
C7—N1—H1N	126.1 (12)	C6—C5—H5	120.3 (11)
C9—N2—H2N	118.1 (11)	C4—C5—H5	118.3 (11)
C9—N2—H3N	122.4 (11)	C5—C6—C7	117.25 (14)
H2N—N2—H3N	119.5 (16)	C5—C6—H6	123.3 (10)
C9—N3—H4N	120.3 (13)	C7—C6—H6	119.5 (10)
C9—N3—H5N	125.3 (13)	N1—C7—C6	130.09 (13)
H4N—N3—H5N	113.9 (18)	N1—C7—C8	107.84 (12)
N1—C1—C2	109.03 (13)	C6—C7—C8	122.07 (13)
N1—C1—H1	122.8 (10)	C3—C8—C7	119.47 (13)
C2—C1—H1	128.2 (10)	C3—C8—C2	134.50 (13)
C1—C2—C8	107.55 (12)	C7—C8—C2	106.03 (12)
C1—C2—S1	125.65 (12)	N2—C9—N3	121.22 (14)
C8—C2—S1	126.55 (11)	N2—C9—S1	121.59 (11)
C4—C3—C8	118.73 (14)	N3—C9—S1	117.19 (11)
C4—C3—H3	121.4 (10)	O3—N4—O1	120.15 (12)
C8—C3—H3	119.8 (10)	O3—N4—O2	120.86 (12)
C3—C4—C5	121.04 (15)	O1—N4—O2	118.99 (12)

C7—N1—C1—C2	−0.19 (17)	C4—C3—C8—C7	0.1 (2)
N1—C1—C2—C8	−0.26 (17)	C4—C3—C8—C2	179.62 (15)
N1—C1—C2—S1	−174.86 (11)	N1—C7—C8—C3	178.96 (13)
C9—S1—C2—C1	−95.95 (14)	C6—C7—C8—C3	−1.2 (2)
C9—S1—C2—C8	90.45 (13)	N1—C7—C8—C2	−0.71 (15)
C8—C3—C4—C5	1.3 (2)	C6—C7—C8—C2	179.17 (13)
C3—C4—C5—C6	−1.7 (2)	C1—C2—C8—C3	−179.01 (16)
C4—C5—C6—C7	0.6 (2)	S1—C2—C8—C3	−4.5 (2)
C1—N1—C7—C6	−179.29 (15)	C1—C2—C8—C7	0.60 (16)
C1—N1—C7—C8	0.58 (16)	S1—C2—C8—C7	175.14 (11)
C5—C6—C7—N1	−179.32 (14)	C2—S1—C9—N2	4.19 (14)
C5—C6—C7—C8	0.8 (2)	C2—S1—C9—N3	−176.06 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.880 (18)	2.036 (19)	2.8290 (16)	149.4 (16)
N2—H2N···O1	0.87 (2)	2.00 (2)	2.8679 (17)	174.2 (16)
N2—H3N···O2ⁱⁱ	0.90 (2)	2.108 (19)	2.9013 (16)	147.0 (16)
N3—H4N···O2	0.90 (2)	2.00 (2)	2.8966 (19)	172.5 (19)
N3—H5N···O3ⁱⁱⁱ	0.89 (2)	2.10 (2)	2.8817 (17)	145.0 (18)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x−1/2, y, −z+1/2; (iii) −x+2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₃S⁺·NO₃⁻
M_r	254.27
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	150
a, b, c (Å)	12.0524 (2), 8.7395 (1), 21.1893 (3)
V (Å³)	2231.91 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.30 × 0.24 × 0.06

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	32180, 2563, 2120
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.04
No. of reflections	2563
No. of parameters	194
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.23

Computer programs: COLLECT (Nonius, 1999), HKL-2000 (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top

S1—C2	1.7448 (14)	N2—C9	1.3076 (19)
S1—C9	1.7566 (15)	N3—C9	1.3162 (19)

C2—S1—C9	102.23 (7)	N2—C9—S1	121.59 (11)
N2—C9—N3	121.22 (14)	N3—C9—S1	117.19 (11)

C9—S1—C2—C1	−95.95 (14)	C2—S1—C9—N2	4.19 (14)
C9—S1—C2—C8	90.45 (13)	C2—S1—C9—N3	−176.06 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.880 (18)	2.036 (19)	2.8290 (16)	149.4 (16)
N2—H2N···O1	0.87 (2)	2.00 (2)	2.8679 (17)	174.2 (16)
N2—H3N···O2ⁱⁱ	0.90 (2)	2.108 (19)	2.9013 (16)	147.0 (16)
N3—H4N···O2	0.90 (2)	2.00 (2)	2.8966 (19)	172.5 (19)
N3—H5N···O3ⁱⁱⁱ	0.89 (2)	2.10 (2)	2.8817 (17)	145.0 (18)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x−1/2, y, −z+1/2; (iii) −x+2, y−1/2, −z+1/2.

Acknowledgements

This work was supported by the Council for Chemical Sciences of the Netherlands Organization for Scientific Research (CW–NWO).

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